CN1578814A - Coating compound for forming titanium oxide film, method for forming titanium oxide film and metal substrate coated with titanium oxide film - Google Patents

Abstract

The present invention provides a coating composition for forming a titanium oxide film, comprising (A) a specific titanium-containing aqueous liquid and (B) at least one compound selected from the group consisting of organic acids and their salts. The present invention also provides a process for forming a titanium oxide film using the coating composition, and a metal substrate coated therewith.

Description

Be used to form the coating composition of titanium dioxide film, the preparation technology of titanium dioxide film and the metal base that scribbles titanium dioxide film

Technical field

The present invention relates to a kind of novel coating composition that is used to form titanium dioxide film, the preparation technology of titanium dioxide film and the metal base that scribbles titanium dioxide film.

Background technology

Metal base such as steel plate, aluminium and aluminium alloy will carry out polytype surface treatment (undercoat) usually to improve erosion resistance, workability etc.

In recent years, required surface-treated steel plate to have higher erosion resistance, and therefore used steel plate to replace cold-rolled steel sheet usually as base material coated with the zinc-base metal.

Usually, adopt chromate treating or phosphatizing coated with the surface treatment of the steel plate of zinc-base metal.

The problem of chromate treating is chromium cpd inherent toxicity.Hexavalent chromium compound particularly, it is extremely deleterious material, is appointed as human carcinogen by IARC (international cancer research institution) and many other community organizations.Particularly, the problem of chromate treating is the stripping of chromic acid in generation chromic salt cigarette in the treating processes, the high expense of sewage treatment equipment needs, the chromate treating coating etc.

Use the common chromate post treatments that needs subsequently of phosphatic phosphatizing such as zinc phosphate, tertiary iron phosphate, thereby relate to the toxicity problem of chromium cpd.In addition, phosphatizing also has the problem of wastewater treatment, metal ion that described waste water comprises reaction accelerator, attracted by the phosphoric acid treatment agent etc. and from the metal stripping handled metal ion caused must carry out slurry treatment.

Japanese unexamined patent publication 1983-224174,1985-50179 and 1985-50180 disclose a kind of coated steel sheet, and each coated steel sheet comprises the steel plate coated with the zinc-base metal as base material, in chromate coating that forms on the base material and the organosilicate coating that forms on chromate coating.Disclosed coated steel sheet has excellent erosion resistance and workability, but has the toxicity problem of the chromium cpd relevant with chromate coating.If there is not chromate coating, then the erosion resistance of coated steel sheet is not enough.

Under a lot of situations, the aluminum or aluminum alloy base material also carries out polytype surface treatment (undercoat), to improve erosion resistance, wetting ability and other character.

Usually, the radiator element in the idle call heat exchanger is made by the aluminum or aluminum alloy base material, because the aluminum or aluminum alloy base material is in light weight and workability and heat conductivity excellence.In air-condition heat exchanger, when cooling operation, water condensation is water droplet and forms the water bridge between radiator element, and the water bridge narrows down air passageways and increases the resistance that air passes through, thereby causes variety of issue, as energy loss, noise, dabble etc.

For addressing these problems, the surface of aluminum or aluminum alloy radiator element is carried out hydrophilic treatment such as boehmite processing, water glass coating, waterborne polymeric coating, form to prevent the water bridge.Yet in highly corrosive environments, the aluminum or aluminum alloy radiator element that hydrophilic treatment is crossed is in about some months internal corrosion, in part because handle the wetting ability of coating.

For preventing the erosion of radiator element, adopt chromate treating to apply undercoat usually, because the advantage of chromate treating is that good erosion resistance can be provided at an easy rate for the aluminum or aluminum alloy base material.Yet chromate treating is attended by the toxic problem of above-mentioned chromium cpd.

For not chromate-containing undercoat material and inner coating process, Japanese unexamined patent publication 1979-24232 discloses with the acid solution that comprises titanium salt, hydrogen peroxide and condensed phosphoric acid and has handled the aluminium surface; Japanese unexamined patent publication 1979-160527 discloses with the alkali aqueous solution that comprises titanium ion and coordination agent and has handled the aluminium surface, washes and use the aqueous solution processing of acid as phosphoric acid then; Japanese unexamined patent publication 1997-20984 discloses a kind of aluminium surface treatment agent, and it comprises phosphate ion, titanium compound and fluorochemical; Disclose the aluminium based metal surface treatment agent with Japanese unexamined patent publication 1997-143752, it comprises condensed phosphate, titanium salt, fluorochemical and phosphite.

Yet these use the undercoat material and the technology of titanium compounds to have such as following problem: the stability of undercoat material is not enough, the erosion resistance of coating than chromate treating coating low, wetting ability not enough and the coating durability not insufficient.

Consider the above description of this area, need a kind of material that forms mineral membrane, it can be used as the undercoat material such as metal bases such as steel plate, aluminium, aluminium alloys, and can form the film of erosion resistance and other character excellence, and does not cause toxicity problem.

Disclosure of the Invention

An object of the present invention is to provide a kind of novel coating composition and form the technology of titanium dioxide film on metal base, described coating composition and technology can form the film of character excellences such as erosion resistance, tackiness, workability.

Another object of the present invention is to provide a kind of metal base that scribbles titanium dioxide film, character excellences such as the erosion resistance of described titanium dioxide film, tackiness, workability.

Other purpose of the present invention and feature are conspicuous from following description.

The invention provides the following new coating composition that is used to form titanium dioxide film, form the technology of titanium dioxide film and scribble the metal base of titanium dioxide film:

1. coating composition that is used to form titanium dioxide film, it comprises (A) a kind of titaniferous aqueous solution, the peptide compounds of its low condenses by making at least a low condenses, titanium hydroxide and the titanium hydroxide that is selected from hydrolyzable titanium compound, hydrolyzable titanium compound mixes with aqueous hydrogen peroxide solution and obtains and (B) at least a compound that is selected from organic acid and salt thereof.

2. the coating composition of project 1, wherein the titaniferous aqueous solution (A) is for by making hydrolyzable titanium compound and/or its low condenses mix the pertitanic acid aqueous solution that obtains with aqueous hydrogen peroxide solution.

3. the coating composition of project 2, wherein the hydrolyzable titanium compound is four titan-alkoxides that are expressed from the next:

Ti(OR) ₄?????????(1)

Wherein R can be identical or different, represents C respectively ₁To C ₅Alkyl.

4. the coating composition of project 2, wherein the low condenses of hydrolyzable titanium compound is condensation degree 2-30 and the compound that obtains from condensation by four titan-alkoxides, four titan-alkoxides of crossing are expressed from the next:

Ti(OR) ₄?????????(1)

Wherein R can be identical or different, represents C respectively ₁To C ₅Alkyl.

5. the coating composition of project 2, wherein the ratio of aqueous hydrogen peroxide solution is 0.1 to 100 weight part of per 10 weight part hydrolyzable titanium compounds and/or its low condenses in hydrogen peroxide.

6. the coating composition of project 2, wherein the titaniferous aqueous solution (A) is for by making hydrolyzable titanium compound and/or its low condenses mix the pertitanic acid aqueous solution that obtains with aqueous hydrogen peroxide solution in the presence of TiO 2 sol.

7. the coating composition of project 6, wherein TiO 2 sol is the aqueous dispersions of anatase titania.

8. the coating composition of project 6, wherein the ratio of TiO 2 sol is 0.01 to 10 weight part in the per 1 weight part hydrolyzable titanium compound of solid and/or its low condenses.

9. the coating composition of project 1, wherein compound (B) is at least a compound that is selected from hydroxycarboxylic acid, hydroxyl organic phosphorous acid, contains carboxyl organic phosphorous acid and these sour salt.

10. the coating composition of project 1, wherein the per 100 weight part solid titaniferous aqueous solution (A) of the ratio of compound (B) are 1 to 400 weight part.

11. the coating composition of project 1, it is the aqueous solution of pH 1 to 10.

12. the coating composition of project 11, it is the aqueous solution of pH 1 to 9.

13. the coating composition of project 1, it further comprises a kind of inorganic phosphate compound.

14. the coating composition of project 1, it further comprises at least a halogenide that is selected from halogen metatitanic acid, halogen titanate, halogen zirconic acid, halogen zirconate, halogen silicic acid and halogen silicate.

15. the coating composition of project 1, it further comprises the water-based organic high molecular compound.

16. a technology that is used to form titanium dioxide film, it comprises the coating composition of metal base being used project 1, and is dry then.

17. a coating metal base material, it comprises a kind of metal base and the film of the coating composition of the project 1 that forms on substrate surface.

18. the coating metal base material of project 17, wherein the dry weight of film is 0.001 to 10g/m ²

19. the coating metal base material of project 17, wherein metal base is formed from steel.

20. the coating metal base material of project 17, wherein metal base is made by aluminum or aluminum alloy.

For achieving the above object, the inventor has carried out extensive studies.The inventor finds that a kind of coating composition can form the film of character excellences such as erosion resistance, tackiness, workability on metal base as a result, this film is suitable for makes undercoat, and described coating composition comprises the titaniferous aqueous solution (A) and as organic acid compound (B).

Finish the present invention based on these new discoveries.

Be used to form the coating composition of titanium dioxide film

The coating composition that is used to form titanium dioxide film of the present invention is the aqueous coating composition, and it comprises the titaniferous aqueous solution (A) and is selected from organic acid and the compound of salt (B).

The aqueous composition of using in coating composition (A) can suitably be selected from the known titaniferous aqueous solution, it can obtain by at least a titanium compound is mixed with aqueous hydrogen peroxide solution, and described titanium compound is selected from the low condenses of low condenses, titanium hydroxide and the titanium hydroxide of hydrolyzable titanium compound, hydrolyzable titanium compound.

The hydrolyzable titanium compound is each titanium compound that contains the one or more hydrolysable group that are bonded directly to titanium atom.Produce titanium hydroxide, water vapour etc. when this compound and water reaction.In the hydrolyzable titanium compound, the group that is bonded to titanium atom can all be a hydrolysable group, or the part group can be hydrolyzed to hydroxyl groups in advance.

Hydrolysable group can produce any group of hydroxyl groups when reacting with water.The example of this group comprise lower alkoxy and with the salifiable group of titanium atom shape.Comprise halogen atom (as the chlorine atom), hydrogen atom, sulfate ion etc. with the example of the salifiable group of titanium atom shape.

Comprise lower alkoxy group and comprise four titan-alkoxides etc. as the example of the hydrolyzable titanium compound of hydrolysable group.

Hydrolyzable titanium compound contain with the salifiable group of titanium shape as hydrolysable group, its exemplary comprises titanium chloride, titanium sulfate etc.

The low condenses of hydrolyzable titanium compound be the hydrolyzable titanium compound from condensation product.In low condenses, the group that is bonded to titanium atom can all be a hydrolysable group, or the part group can be hydrolyzed to hydroxyl groups in advance.

The aqueous solution that the example of the low condenses of titanium hydroxide comprises titanium chloride, titanium sulfate etc. with as the alkali aqueous solution of ammonium or caustic soda react the titanic hydroxide (titanic hydroxide gel) that obtains

The condensation degree of the low condenses of hydrolyzable titanium compound or the low condenses of titanium hydroxide is 2 to 30, is preferably 2 to 10.

The aqueous solution (A) can be the known titaniferous aqueous solution that obtains by above-mentioned titanium compound and aqueous hydrogen peroxide solution reaction.The object lesson of this aqueous solution comprises following:

(1) the pertitanic acid aqueous solution of describing among Japanese unexamined patent publication 1988-35419 and the 1989-224220, its preparation method is to add aqueous hydrogen peroxide solution in the hydrogel of titanium dioxide or the water-sol;

(2) yellow of describing among Japanese unexamined patent publication 1997-71418 and the 1998-67516 that is used to form titanium dioxide film, transparent, the thickness aqueous solution, its preparation method is: the aqueous solution that makes titanium chloride, titanium sulfate etc. with as the alkali aqueous solution of ammonium or caustic soda react, be settled out titanic hydroxide gel, be called titanic hydroxide; By decant separation of hydrogen titanium oxide gel; Wash isolating gel with water; With add aqueous hydrogen peroxide solution to gel;

(3) aqueous solution of the formation titanium dioxide film of describing among Japanese unexamined patent publication 2000-247638 and the 2000-247639, its preparation method is: add aqueous hydrogen peroxide solution and prepare the titanium peroxide hydrate in the aqueous solution such as inorganic titanium compound such as titanium chloride, titanium sulfate; In the titanium peroxide hydrate, add alkaline matter; The solution that placement or heating obtain is so that titanium peroxide hydrated polymer precipitation; Dissolved constituent except that anhydrating; And make hydrogen peroxide work.

Preferably, the titaniferous aqueous solution (A) is by making the mixed pertitanic acid aqueous solution (A1) that gets of hydrolyzable titanium compound and/or its low condenses and aqueous hydrogen peroxide solution.

The example of particularly preferred titanium compound is four titan-alkoxides that following formula is represented

Ti(OR) ₄?????????(1)

Wherein R can be identical or different, represents C respectively ₁To C ₅Alkyl.The C that represents by R ₁To C ₅The example of alkyl comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl etc.

The low condenses of titanium compound be preferably formula (1) compound from condenses, condensation degree is 2 to 30, preferred 2 to 10.

Hydrolyzable titanium compound and/or its low condenses (hereinafter this compound and/or its low condenses abbreviate " hydrolyzable titanium compound (T) " as) with respect to formula (1), the ratio of aqueous hydrogen peroxide solution is preferably 0.1 to 100 weight part in the per 10 parts of hydrolyzable titanium compounds of hydrogen peroxide (T), is preferably 1 to 20 weight part especially.The aqueous hydrogen peroxide solution (in hydrogen peroxide) that is less than 0.1 weight part causes the formation of pertitanic acid not thorough, produces opaque precipitation.On the other hand, if use has still unreacted of part hydrogen peroxide probably more than the aqueous hydrogen peroxide solution (in hydrogen peroxide) of 100 weight parts, and when storing, emit deleterious active oxygen.

Concentration of hydrogen peroxide in the aqueous hydrogen peroxide solution but considers to be convenient to operation, preferred 3 to 40 weight % without limits.

The preparation of the pertitanic acid aqueous solution is usually by mixing hydrolyzable titanium compound (T) and aqueous hydrogen peroxide solution about 10 minutes to about 20 hours under about 1 to 70 ℃.If desired, also can add water-soluble solvents such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether.

By that analogy, the pertitanic acid aqueous solution (A1) can obtain by following mechanism: when hydrolyzable titanium compound (T) when mixing with aqueous hydrogen peroxide solution, described compound and water generation hydrolysis, and form the titanium compound of hydroxyl.Immediately hydrogen peroxide is coordinated to then in the titanium compound of hydroxyl to form pertitanic acid.The pertitanic acid aqueous solution is highly stable in room temperature, and can preserve for a long time.

Also preferred a kind of pertitanic acid aqueous solution (A2), its preparation method is that hydrolyzable titanium compound (T) is mixed in the presence of TiO 2 sol with aqueous hydrogen peroxide solution, because this solution has the package stability of improvement and can form erosion resistance and the improved titanium dioxide film of other character.Improved reason is presumed as follows: in preparation aqueous solution process, hydrolyzable titanium compound (T) is adsorbed on the TiO 2 sol particle, and is chemically bound in the hydroxyl groups that produces on the particle surface by condensation.In addition, the hydrolyzable titanium compound carries out from condensation and is converted into high-molecular weight compounds.Then, high-molecular weight compounds mixes with aqueous hydrogen peroxide solution, thereby obtains the stable aqueous solution, and it does not obviously have gelling or multiviscosisty in storage process.

TiO 2 sol comprises amorphous titania particle or the anatase titania particle that is dispersed in the water.As TiO 2 sol, from the aqueous dispersions of the preferred anatase titania of erosion-resisting angle.Outside dewatering, TiO 2 sol can comprise aqueous organic solvent such as alcoholic solvent or alcohol ether solvents.

TiO 2 sol can be known, as makes the titanium dioxide agglomerate disperse the amorphous titania dispersion of particles liquid that obtains in water, or obtains the dispersion liquid of anatase titania particle in water by the calcinated titanium dioxide agglomerate.Amorphous titania can be by being converted into anatase titania at the temperature lower calcination that is not less than the anatase octahedrite Tc, usually in the temperature calcining that is not less than 200 ℃.The example of titanium dioxide agglomerate comprises the agglomerate that (1) obtains by hydrolysis inorganic titanium compound such as titanium sulfate or titanyl sulfate, (2) agglomerate that obtains by hydrolysis organic titanic compound such as alkyl dioxide, (3) by hydrolysis or in and the agglomerate that obtains of the solution of halogenated titanium such as titanium tetrachloride etc.

Commercially available TiO 2 sol comprises, " TKS-201 " (trade mark of TEICA Corp. for example, mean particle size is the water-sol of the anatase titania particle of 6nm), " TKS-203 " (trade mark of TEICA Corp., the water-sol of the anatase titania particle of mean particle size 6nm), " TA-15 " (Nissan Chemical Industries, Ltd. trade mark, the water-sol of anatase titania particle) and " STS-11 " (Ishihara Sangyo Kaisha, Ltd. trade mark, the water-sol of anatase titania particle).

When mixing with aqueous hydrogen peroxide solution, the amount of the TiO 2 sol of use per 1 weight part hydrolyzable titanium compound (T) usually is 0.01 to 10 weight part solid, preferred 0.1 to 8 weight part solid at hydrolyzable titanium compound (T).Be less than 0.01 parts by weight of titanium oxide colloidal sol and can not realize adding the effect of TiO 2 sol, be i.e. the improvement of the stability in storage of coating composition and titanium dioxide film erosion resistance.On the other hand, weaken the film forming character of coating composition more than the colloidal sol of 10 weight parts.Therefore, should not use above-mentioned scope amount in addition.

The titaniferous aqueous solution (A) can be not more than the dispersion form use of the TiO 2 particles of 10nm with mean particle size.The preparation method of this dispersion makes hydrolyzable titanium compound (T) choose wantonly in the presence of TiO 2 sol with aqueous hydrogen peroxide solution to mix, and makes the pertitanic acid aqueous solution that obtains through heat-treated or autoclaving being not less than under 80 ℃ the temperature then.Dispersion is generally translucent appearance.

If thermal treatment or autoclaving are carried out in the temperature that is lower than 80 ℃, the crystallization of titanium dioxide can not fully be carried out.The granularity of the TiO 2 particles that obtains by thermal treatment or autoclaving is not more than 10nm, and preferred 1 to 6nm.If the coating composition film forming character that the granularity of TiO 2 particles greater than 10nm, obtains is so low so that dry weight is 1g/m ²Or crackle appears in bigger film.

When as the titaniferous aqueous solution (A), the aqueous solution (A1) forms the amorphous titania film that comprises small amount of hydroxyl groups group usually under above-mentioned drying conditions.The amorphous titania film has the advantage of higher airbond character.When the titaniferous aqueous solution (A2) was used as the titaniferous aqueous solution (A), this solution formed the anatase titania film that comprises small amount of hydroxyl groups group usually under above-mentioned drying conditions.

In coating composition of the present invention, at least a main effect that is selected from the compound (B) of organic acid and salt thereof is to improve the erosion resistance of gained film and the stability in storage of coating composition.

Organic acid example as compound (B) comprises organic carboxyl acid such as acetate, oxalic acid, oxyacetic acid, lactic acid, oxysuccinic acid, citric acid, tartrate and gluconic acid; Organic sulfonic acid such as methylsulfonic acid, ethyl sulfonic acid and tosic acid; Organic-sulfinic acid such as 2-amino-ethyl-sulfinic acid and p-methylphenyl-sulfinic acid; Organic nitro-compound such as Nitromethane 99Min., nitroethane, nitropropionic acid, Nitrocatechol, 2-nitro-resorcinol and nitrobenzoic acid; Phenols such as phenol, catechol, Resorcinol, quinhydrones, pyrogaelol, Whitfield's ointment, gallic acid, phenylformic acid, thiophene, 2-aminothiophene and 4-ethylthiophene; Organic phosphoric acid compound such as 1-methylol-1,1-di 2 ethylhexyl phosphonic acid, 1-hydroxyethyl-1,1-di 2 ethylhexyl phosphonic acid, 1-hydroxypropyl-1,1-di 2 ethylhexyl phosphonic acid, nitrilo (amino) trimethylene phosphonic, nitrilo (amino) triethylene phosphonic acids, nitrilo (amino) Sanya propyl phosphonous acid, ethylenediamine tetramethylene phosphonic acid, ethylenediamine tetraacetic ethylidene phosphonic acids, ethylenediamine tetraacetic propylidene phosphonic acids, N, two (the 2-phosphoric acid ethyl) azanols of N-, N, hydrolyzate, 2-hydroxy dioxetane phosphorus guanidine-acetic acid and the 2-phosphonic acids butane-1 of two (the 2-phosphoric acid methyl) azanols of N-, 2-hydroxyethyl dimethyl phosphonate, 2, the 4-tricarboxylic acid; Deng.

Organic acid salt as compound (B) can form by add alkali cpd in above-mentioned any organic acid.The example of alkali cpd comprises the organic or inorganic alkali cpd that contains lithium, sodium, potassium, ammonium etc.

Preferably, compound (B) is water-soluble.

As compound (B), especially preferably use at least a following compound that is selected from: hydroxycarboxylic acid, as oxyacetic acid, lactic acid, oxysuccinic acid, citric acid, tartrate and gluconic acid; The organic phosphorous acid of hydroxyl, as 1-methylol-1,1-di 2 ethylhexyl phosphonic acid, 1-hydroxyethyl-1,1-di 2 ethylhexyl phosphonic acid, 1-hydroxypropyl-1,1-di 2 ethylhexyl phosphonic acid; Carboxylic organic phosphorous acid, as 2-phosphinylidyne butane-1,2,4-tricarboxylic acid, 2-HPAA; And salt, because these compounds show excellent effect to the erosion resistance of the stability in storage of coating composition, the coating that obtains etc.

With respect to the titaniferous aqueous solution (A), the per 100 weight part solid titaniferous aqueous solution (A) of the ratio of compound (B) are preferably about 1 to 400 weight part, more preferably from about 10 to 200 weight parts.The compound (B) that use is less than 1 weight part causes erosion resistance low, and if use to surpass the compound (B) of 400 weight parts, will weaken the film forming character of coating composition and reduce erosion resistance.Therefore, should not use specialized range ratio in addition.

The preparation method of coating composition of the present invention makes the titaniferous aqueous solution (A) mix with at least a compound (B), and described compound (B) is selected from organic acid and salt thereof.

By that analogy, in coating composition of the present invention, the acid ion of organic acid group and titanium ion coordination are so that form complex structure in the compound (B) between acid ion and titanium ion.The example of this organic acid group comprises groups such as hydroxyl, carboxyl, phosphorous acid.By simple blending ingredients (A) and (B), allow mixture leave standstill then, (20 ℃) were placed about 5 minutes to about 1 hour as at room temperature, can easily form complex structure.Mixture can be about 1 to 30 minute of 30 to 70 ℃ of heating according to appointment to form complex structure.

Coating composition of the present invention is the stable aqueous solution, is generally pH 1 to 10.When be in acidity or weakly alkaline, preferred pH 1 to 9, more preferably pH 1 to 7, further more preferably pH1 is to 5 the time, said composition has good especially stability in storage.

Coating composition optionally contains for example methyl alcohol, ethanol, Virahol, ethylene glycol, propylene glycol or similar hydrophilic solvent.As required, coating composition used water or hydrophilic solvent dilution.

As required, coating composition can comprise the inorganic phosphate compound to improve the erosion resistance of gained film.

Spendable inorganic phosphate compound comprises, for example, and single phosphoric acid such as phosphorous acid, strong phosphoric acid, triphosphoric acid, ortho phosphorous acid, diphosphanetetroic acid, three metaphosphoric acids, diphosphorous acid, bisphosphate, pyrophosphorous acid, tetra-sodium, metaphosphorous acid, metaphosphoric acid and ortho-phosphoric acid; Single phosphoric acid derivatives and salt; Condensed phosphoric acid such as tripolyphosphate, four phosphoric acid and six phosphoric acid; Condensed phosphoric acid derivative and salt etc.These compounds can be used singly or in combination.In addition, these phosphate cpds can be the form with the salt of alkali cpd.The example of alkali cpd comprises the organic or inorganic alkali cpd that contains lithium, sodium, potassium, ammonium etc.

Preferred these inorganic phosphate compounds are water-soluble.

Particularly preferred phosphate cpd is ortho-phosphoric acid, trisodium phosphate, tripoly phosphate sodium STPP, sodium tetraphosphate, metaphosphoric acid, ammonium metaphosphate, Sodium hexametaphosphate 99 etc., because these phosphate cpds significantly improve the stability in storage of coating composition and the erosion resistance of gained film etc.

When using the inorganic phosphate compound, with respect to the titaniferous aqueous solution (A), the per 100 weight part solid titaniferous aqueous solution (A) of the ratio of phosphate cpd are preferably about 1 to 400 weight part, more preferably 10 to 200 weight parts.

As required, coating composition of the present invention can comprise at least a halogenide that is selected from halogen metatitanic acid, halogen titanate, halogen zirconic acid, halogen zirconate, halogen silicic acid and halogen silicate, with the further erosion resistance of improving the gained film.

The example of the halogen in these halides comprises fluorine, chlorine, iodine etc.Wherein preferred especially fluorine is with the high corrosion resistance of the excellent storage stability that realizes coating composition and gained film and moisture resistance etc.Halide salts is, for example the salt that forms with sodium, potassium, lithium, ammonium etc.Wherein preferred potassium, sodium and ammonium.

Preferred halid example comprises halogen metatitanic acids such as hydrofluotitanic acid; Halogen such as potassium fluotitanate, ammonium titanium fluoride titanate; Halogen zirconic acids such as fluorine zirconic acid; Halogen such as ammonium fluozirconate, potassium fluozirconate zirconate; Halogen silicic acid such as silicofluoric acid; Halogen silicates such as Sodium Silicofluoride, ammonium silicofluoride, potassium silicofluoride etc.

When above any halogenide was used for coating composition of the present invention, the per 100 weight part solid titaniferous aqueous solution (A) of its ratio were preferably about 1 to 400 weight part, more preferably from about 10 to 200 weight parts.

As required, coating composition of the present invention can comprise that a kind of water-based organic high molecular compound is with the film forming character of improving coating composition, to tackiness of external coating (EC) etc.

The water-based organic high molecular compound can be the aqueous solution, aqueous dispersions or emulsion form.Described compound can be by currently known methods dissolving in water, dispersion or emulsification.

The example of water-based organic high molecular compound comprises that functional group's (as in hydroxyl, carboxyl, amino, imido grpup, sulfide, phosphine etc. at least a) self can make compound dissolution or be scattered in compound and the part or all of compound that has been neutralized of functional group wherein in the water.When compound is acidic resins when containing carboxy resin, the neutralization of compound can be used thanomin, triethylamine or similar amine compound; Aqueous ammonium; Lithium hydroxide, sodium hydroxide, potassium hydroxide or similar alkali metal hydroxide etc.When compound is a basic resin when containing polyimide resin, the neutralization of compound can be used acetate, lactic acid or similar lipid acid, phosphoric acid or similar mineral acid etc.

The example of water-based organic high molecular compound comprises Resins, epoxy, phenol resins, acrylic resin, urethane resin, polyvinyl alcohol resin, the copolymers of unsaturated carboxylic acids resin that contains polyoxyalkylene hydrocarbon chain resin, olefinic polymerization, nylon resin, Polyglycerine, carboxymethyl cellulose, Walocel MT 20.000PV, Natvosol etc.

Preferably, described compound is a Resins, epoxy, phenol resins, acrylic resin, urethane resin, polyvinyl alcohol resin, contains polyoxyalkylene hydrocarbon chain resin, the polymerisable copolymers of unsaturated carboxylic acids resin of alkene etc.

When described compound highly-hydrophilic, the composition that obtains can form the film that has high corrosion resistance and high-hydrophilic simultaneously, thereby is fit to be used for the radiator element made by aluminum or aluminum alloy as hydrophilic reagent.

The example of preferred Resins, epoxy comprises cation epoxy resin, and it obtains by add amine in Resins, epoxy; Modified epoxy such as acrylic modified epoxy resin, polyurethane modified epoxy resin etc.The example of cation epoxy resin comprises the affixture of epoxy compounds and following material: the mixture of one-level monoamine or polyamine, secondary monoamine or polyamine, firsts and seconds polyamine (for example, referring to the US patent No. 3984299); The affixture of epoxy compounds and secondary monoamine or polyamine, described amine have the primary amine group (for example, referring to the US patent No. 4017438) of ketoimineization; The esterification reaction product of epoxy compounds and oxy-compound, described oxy-compound have the primary amine group (for example, referring to Japanese unexamined patent publication 1984-43013) of ketoimineization etc.

The example of preferred epoxy compounds comprises that those number-average molecular weights are 400 to 4000, particularly 800 to 2000, and epoxy equivalent (weight) is 190 to 2000, and 400 to 1000 compound particularly.These epoxy compoundss can obtain by for example making the reaction of polyphenolic substance and epichlorohydrin.The example of polyphenolic substance comprises two (4-hydroxy phenyls)-2,2-propane, 4,4-dihydroxy benzophenone, two (4-hydroxy phenyl)-1,1-ethane, two (4-hydroxy phenyl)-1,1-Trimethylmethane, two (4-hydroxyl tert-butyl-phenyl)-2,2-propane, two (2 hydroxy naphthalene base) methane, 1,5-dihydroxy naphthlene, two (2, the 4-dihydroxy phenyl) methane, four (4-hydroxy phenyl)-1,1,2,2-ethane, 4,4-dihydroxy-diphenyl sulfone, phenol type phenolic varnish, cresols type phenolic varnish etc.

Preferred phenol resins comprises those materials by the water-soluble high-molecular compound preparation, and described water-soluble high-molecular compound is by the phenol component and formaldehyde carries out addition by heating in the presence of catalysts and condensation obtains.Spendable starting phenol component be bifunctional phenol compound, tri-functional phenols compound, four or higher official can phenolic compound etc.Bifunctional phenol compound's example comprises ortho-cresol, p-cresol, p-tert-butylphenol, p-ethyl phenol, 2,3-xylenol, 2,5-xylenol etc.The example of tri-functional phenols compound comprises phenol, meta-cresol, m-ethylphenol, 3,5-xylenol, meta-methoxy phenol etc.The example of four sense phenolic compound comprises dihydroxyphenyl propane, Bisphenol F etc.These phenolic compound can be used alone or in combination.

Preferred acrylic resin comprises for example having the monomeric homopolymer or the multipolymer of hydrophilic radical such as carboxyl, amino or hydroxyl; Comprise the monomer of hydrophilic radical and the multipolymer of other copolymerisable monomer etc.These resins obtain by emulsion polymerization, suspension polymerization or solution polymerization, optionally are converted into water-base resin by neutralization subsequently.If desired, further modification of the resin that obtains.

The example that contains carboxylic monomer comprises vinylformic acid, methacrylic acid, maleic acid, MALEIC ANHYDRIDE, Ba Dousuan, methylene-succinic acid etc.

The example of nitrogen containing monomer comprises (methyl) vinylformic acid-N, N-dimethylamino ethyl ester, (methyl) vinylformic acid-N, N-diethylamino ethyl ester, (methyl) vinylformic acid-(methyl) acrylic acid nitrogenous alkyl esters such as N-tertiary butyl amino ethyl ester; Acrylamide, Methacrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-methoxyl methyl (methyl) acrylamide, N-fourth oxygen methyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-dimethylamino-propyl (methyl) acrylamide, N, polymerizable acid amides such as N-dimethylaminoethyl (methyl) acrylamide; Aromatic nitrogen-contg monomers such as 2-vinyl pyridine, 1-vinyl-2-pyrrolinone, 4-vinylpridine; Allylamine etc.

The monomeric example of hydroxyl comprises (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid-2, the monoesters of polyvalent alcohol such as 3-dihydroxyl butyl ester, (methyl) vinylformic acid-4-hydroxyl butyl ester, polyethyleneglycol (methyl) acrylate and acrylic or methacrylic acid; The monoesters of polyvalent alcohol and acrylic or methacrylic acid and 6-caprolactone carry out compound that ring-opening polymerization obtains etc.

Other polymerisable monomer comprises, for example (methyl) acrylic acid C such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) ethyl acrylate, (methyl) vinylformic acid n-octyl, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid stearyl, (methyl) vinylformic acid isooctadecane base ester ₁To C ₂₄Alkyl ester; Vinylbenzene; Vinyl-acetic ester etc.These compounds can be used alone or in combination.

Term as used herein " (methyl) acrylate " is meant acrylate or methacrylic ester.

Preferred urethane resin comprises those materials by the following steps preparation: make the urethane resin that is obtained by polyvalent alcohol (as polyester polyol or polyether glycol) and vulcabond carry out chain extension, optionally in the presence of low molecular compound, carry out as chain extension agent, described low molecular compound has at least two active hydrogen atoms, as glycol or diamines; Urethane resin stably is dispersed or dissolved in the water.These urethane resins have been examined among patent publication No. 1967-24192,1967-24194,1967-5118,1974-986,1974-33104,1975-15027 and the 1978-29175 open in for example Japan.

Urethane resin can stably be dispersed or dissolved in the water by for example following method:

(1) make radical ion such as hydroxyl, amino or carboxyl introduce the side chain or the end of urethane resin, to give resin with wetting ability; With resin is dispersed or dissolved in the water by self-emulsifying.

(2) making the urethane resin of finishing reaction or terminal isocyanate group group hold the urethane resin of envelope to force with blocking agent with emulsifying agent and mechanical shear stress is dispersed in the water.The example of spendable blocking agent comprises oxime, alcohol, phenol, mercaptan, amine or sodium pyrosulfate.

(3) urethane resin, water, emulsifying agent and the chain extension agent of isocyanic ester end envelope are mixed; Make resin be converted into macromolecule resin in the time of with use mechanical shear stress dispersion resin.

(4) urethane resin is dispersed or dissolved in the water, described urethane resin uses water-soluble polyol such as polyoxyethylene glycol to prepare as initial polyvalent alcohol.

The water-base resin that disperses or dissolves the urethane resin preparation by aforesaid method can be used singly or in combination.

The spendable vulcabond of synthesis of polyurethane resin comprises aromatic, alicyclic or aliphatic vulcabond.The object lesson of these vulcabond comprises hexamethylene diisocyanate, tetramethylene diisocyanate, 3,3 '-dimethoxy-4 ', 4 '-biphenylene vulcabond, to eylylene diisocyanate, between eylylene diisocyanate, 1,3-(two isocyanato-methyl) pimelinketone, 1,4-(two isocyanato-methyl) pimelinketone, 4,4 '-two isocyanato-pimelinketone, 4,4 '-methylene-bis (cyclohexyl isocyanate), isophorone diisocyanate, 2,4-toluylene group diisocyanate, 2,6-toluylene group diisocyanate, to phenylene vulcabond, diphenylmethanediisocyanate, the metaphenylene vulcabond, 2, the 4-naphthalene diisocyanate, 3,3 '-dimethyl-4,4 '-biphenylene vulcabond, 4,4 '-biphenylene vulcabond etc.Wherein, particularly preferably be 2,4-toluylene group diisocyanate, 2,6-toluylene group diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.

The product of commercially available urethane resin comprises, for example, and " Hydran HW-330 ", " Hydran HW-340 " and " Hydran HW-350 " (Dainippon Ink and Chemicals, the trade mark of Inc.); " Superflex 100 ", " Superflex 150 " and " Superflex F-3438D " (Dai-ichi Kogyo Seiyaku Co., the trade mark of Ltd.) etc.

Preferred polyvinyl alcohol resin is that those saponification degs are not less than 87% material, particularly saponification deg and are not less than 98%, are called thorough saponified polyvinyl alcohol.In addition, the number-average molecular weight of preferred resin is 3,000 to 100,000.

The spendable polyoxyalkylene hydrocarbon chain resin that contains comprises the resin that contains polyoxyethylene chain or polyoxypropylene chains.The example of these resins comprises polyoxyethylene glycol, polypropylene glycol, wherein polyethylene oxide chain and polyoxytrimethylene chain are bonded the block polyoxyalkylene glycol that forms block etc.

Be the dispersible or water soluble resins of at least a or two water preferably as the polymerisable copolymers of unsaturated carboxylic acids resin of alkene, i.e. (i) ethene, propylene or similar alkene and (methyl) vinylformic acid, maleic acid or the similarly multipolymer of polymerizable unsaturated carboxylic acid; (ii) a kind of cross-linked resin, the aqueous dispersions by polymerisable unsaturated compound being joined above-mentioned multipolymer is to carry out emulsion polymerization, and intergranular is crosslinked then obtains.

Multipolymer (i) comprises at least a alkene and at least a polymerisable unsaturated carboxylic acid.As monomer component, preferred copolymer comprises 3 to 60 weight %, the unsaturated carboxylic acid of preferred 5 to 40 weight % or acid.Multipolymer can be by being dispersed in the water with the acidic-group in the alkaline matter neutralized copolymer.

Emulsion polymerization and intergranular are crosslinked to prepare cross-linked resin (ii) to carry out to add polymerisable unsaturated compound in the aqueous dispersions of above-mentioned multipolymer, described polymerisable unsaturated compound can be, any vinyl monomer of listing in for example dispersible at above water or water soluble acrylic resin's the description.These vinyl monomers can be used singly or in combination.

When in composition of the present invention, making the use organic high molecular compound, consider from the angle of the erosion resistance of the stability of coating composition and gained titanium dioxide film, the per 100 weight part solid titaniferous aqueous solution (A) of the ratio of water-based organic high molecular compound are preferably 10 to 2,000 weight part, preferred especially 100 to 1,000 weight parts.

As required, coating composition of the present invention can comprise divalence or more the high price Al, Ca, Ti, V, Mn, Co, Fe, Cu, Zn, Zr, Nb, Mo, Ta, W plasma, with resistance to acid and the alkali-resistivity of improving the gained film.

If desired, coating composition of the present invention can further comprise ammonium, alkaline organic compound, alkali metal hydroxide, alkaline earth metal hydroxides or similar alkaline neutraliser.Preferred alkaline organic compound comprises that as thanomin and triethylamine, preferably alkali metal hydroxide comprises, for example lithium hydroxide, sodium hydroxide, potassium hydroxide etc.

If desired, coating composition can comprise additive such as thickening material, antiseptic-germicide, rust remover, TiO 2 sol, titania powder, pigment extender, rust cleaning pigment, coloured pigment, tensio-active agent etc.Spendable rust remover comprises, as Weibull, phytinic acid, benzotriazole, ammonium meta-vanadate, zirconium carbonate ammonium etc.Spendable pigment extender comprises, as mica, talcum, silicon-dioxide, fine silica powder, barium oxide, clay etc.The adding of pigment extender is favourable, because when external coating (EC) forms, pigment extender is by the tackiness of anchor effect improvement with external coating (EC).

Form the technology and the metal base that scribbles titanium dioxide film of titanium dioxide film

The technology that the present invention forms titanium dioxide film comprises uses coating composition of the present invention to metal base, dry then.This technology produces the metal base that scribbles titanium dioxide film.The coating metal base material itself can be used as the antirust coating metal base.

The employed metal base of technology of the present invention can be any base material that has a metallic surface at least.Spendable base material comprises that those surfaces are by iron, aluminium, magnesium, zinc, copper, tin or comprise the base material that the alloy of any of these metal is made.Particularly preferably be substrate of steel plate and aluminum or aluminum alloy base material.

The example of substrate of steel plate comprises hot-dip galvanized steel sheet, electrogalvanizing steel plate, plating iron zinc alloy steel plate, nickel and zinc alloy steel plate, plate golding aluminium zinc alloy steel plate etc.The example of plate golding aluminium zinc alloy steel plate comprises the base material of those commercially available commodity " Galvalium " or " Galfan " by name.What also can be used as substrate of steel plate handles the zinc-base Metal plating zinc steel plate of handling as chromium processing, zinc phosphate processing or complex oxide film for experiencing chemical transformation.In addition, the steel plate subassembly can be used as substrate of steel plate.

The typical example of aluminum or aluminum alloy base material includes but not limited to heat exchanger fin.Can be knownly as the heat exchanger fin of base material, can be a separating member before being assembled into heat exchanger or a member that is assembled into heat exchanger.

Can use any known technology that coating composition of the present invention is applied to metal base, as dip coated, spray coating, spraying, roller coat and electropaining.Usually preferred composition is heated dry about 2 seconds to about 30 minutes, and heating condition is that the top temperature that base material reaches is about 60 to 250 ℃.

The amount of coating composition to be administered is preferably about 0.001 to 10g/m of dry film weight ², more preferably 0.1 arrive 5g/m ²If amount is less than 0.001g/m ², character such as the erosion resistance of gained film, water resisting property are poor, and if measure more than 10g/m ², the gained film crackle occurs or erosion resistance reduces.Therefore, should not use specialized range amount in addition.

Like this, technology of the present invention produces titanium dioxide film on metal base, and it has excellent erosion resistance, tackiness, workability, anti-impression of the hand etc.

Coating composition can be applied to non-metallic substrate and the dry titanium dioxide film that forms.

The example of non-metallic substrate includes but not limited to plastic basis material, and its combination by polyvinyl chloride (PVC) RESINS, polyethylene terephthalate, acrylic resin, silicone resin, vibrin, fluoro-resin, Resins, epoxy, polyvinyl resin, nylon resin, butyral resin, celluosic resin, phenol resins or two or more these resins is made; Glass, inorganic substrates such as cement; Timber, paper, fiber or similar paper pulp base material; Carry out surface treatment or these plastic basis materials of handling, inorganic substrate or paper pulp base material etc. with priming paint.

Can coating composition be applied to these base materials by already known processes, as dip coated, spray coating, spraying, roller coat or electropaining.Usually preferred composition is heated dry about 2 seconds to about 30 minutes, and heating condition is that the top temperature that base material reaches is about 20 to 250 ℃.The amount of coating composition to be administered is preferably about 0.001 to 10g/m of dry film weight ²

Can on the base material of the titanium dioxide film that scribbles coating composition of the present invention, form external coating (EC).Forming the overcoating combinations thing can be selected from according to specifying purpose to be selected from multiple coating composition.The example that is used to form the coating composition of external coating (EC) comprises the composition that forms lubricant film, the composition that forms the high corrosion resistance film, paint base composition, colored overcoat compositions etc.Also can use and the dry composition of lubricant film, the composition or the paint base composition of formation high corrosion resistance film of forming, on the coating that obtains, further use colored overcoat compositions then.

The aluminum or aluminum alloy base material that scribbles coating composition of the present invention has character such as excellent erosion resistance, wetting ability, tackiness, workability.When using rayed, the wetting ability of base material is further improved.

The aluminum or aluminum alloy base material of the film that forms when the composition that scribbles by coating of the present invention is during as heat exchanger fin, and if desired, described film can scribble one deck hydrophilic coating.

Hydrophilic coating has water-wetted surface, full intensity, high waterproof and to the good tackiness of undercoat.Hydrophilic coating preferably forms by using with dry hydrophilic composition.

Hydrophilic composition preferably comprises the tackiness agent that forms hydrophilic film.The preferred tackiness agent that forms hydrophilic film comprises, as (1) a kind of organic binder resin, it mainly comprises a kind of organic hydrophilic resin and optionally comprises a kind of linking agent, (2) a kind of organic resin/colloidal silica tackiness agent, it mainly comprises a kind of organic hydrophilic resin and colloidal silica and optionally comprises a kind of linking agent, (3) water glass binder, it is made as the mixture of main component by alkaline silicate and negatively charged ion or non-ionic water organic resin, or the like.In these tackiness agents, preferred especially organic binder resin (1) and organic resin/colloidal silica tackiness agent (2).

Implement preferred plan of the present invention

Provide following production example, embodiment and comparative example to be used to illustrate in greater detail the present invention, do not limit the scope of the invention.In following examples, umber and per-cent are all by weight.

The preparation of the titaniferous aqueous solution (A)

Production example 1

Ammonia soln 10% is added drop-wise in the 500cc aqueous solution so that the titanium hydroxide precipitation, and wherein the 500cc aqueous solution obtains by 60% titanium tetrachloride aqueous solution with distilled water diluting 5cc.Precipitation is with distillation washing, mixes with 30% aqueous hydrogen peroxide solution of 10cc and stirs, and obtains the yellow translucent thick liquid that 70cc comprises pertitanic acid (the titaniferous aqueous solution (1)), and its solids content is 2%.

Production example 2

Stir more than 1 hour at 20 ℃, the mixture of 10 parts of tetraisopropoxy titaniums and 10 parts of Virahols is added drop-wise in the mixture of 10 part of 30% aqueous hydrogen peroxide solution and 100 parts of deionized waters.Then, the mixture that obtains wore out 2 hours at 25 ℃, obtained yellow translucent little heavy-gravity pertitanic acid aqueous solution (the titaniferous aqueous solution (2)), and its solids content is 2%.

Production example 3

The step of duplication of production embodiment 2, different is to replace tetraisopropoxy titanium with 10 part of four titanium n-butoxide, obtains the titaniferous aqueous solution (3), its solids content is 2%.

Production example 4

The step of duplication of production embodiment 2, different is to replace tetraisopropoxy titanium with 10 parts of tetraisopropoxy titanium tripolymers, obtains the titaniferous aqueous solution (4), its solids content is 2%.

Production example 5

The step of duplication of production embodiment 2, different be to use 3 times of amount aqueous hydrogen peroxide solutions and 50 ℃ of droppings carry out more than 1 hour and subsequently 60 ℃ aging 3 hours.Obtain the titaniferous aqueous solution (5) like this, its solids content is 2%.

Production example 6

95 ℃ of titaniferous aqueous solution of obtaining of heating production examples 36 hours, obtain the slightly yellow translucent titanium oxide dispersion (the titaniferous aqueous solution (6)) of white, its solids content is 2%.

Production example 7

Stir more than 1 hour at 10 ℃, the mixture of 10 parts of tetraisopropoxy titaniums and 10 parts of Virahols is added drop-wise in the mixture of 5 parts of (solid) " TKS-203 " (trade mark of TEICA Corp., the water sol of the anatase titania particle of mean particle size 6nm), 10 part of 30% aqueous hydrogen peroxide solution and 100 parts of deionized waters.Then, the gained mixture wore out 24 hours at 10 ℃, obtained yellow translucent little heavy-gravity titaniferous aqueous solution (7), and its solids content is 2%.

The preparation of water-based organic high molecular compound

Production example 8

In 1 liter of four neck flask that thermometer, agitator, condenser and dropping funnel are installed, add 180 parts of Virahols, and use purging with nitrogen gas.Regulate in the flask temperature to 85 ℃ then.In surpassing about 2 hours, drip 140 parts of ethyl propenoates, 68 parts of methyl methacrylates, 15 parts of vinylbenzene, 15 parts of N-n-butoxy Methacrylamides, 38 parts of vinylformic acid 2-hydroxyl ethyl esters and 24 parts of vinylformic acid and 6 parts as 2 of catalyzer, the monomer mixture of 2 '-azo two (2, the 4-methyl pentane nitrile).After dripping end, under uniform temp, continue reaction 5 hours.The result obtains colourless semi-transparent resin solution, and its condensation degree is near 100%, solids content be about 63% and acid number be about 67mgKOH/g.Resin solution (500 parts) mixes with 108 parts of dimethylaminoethanols.Add after the water, thoroughly stir the mixture to obtain water-borne acrylic resin dispersion liquid (C1), its solids content is 30%.

Production example 9

In the reactor that agitator, reflux exchanger, thermometer and dropping funnel are installed, add 1, " Epikote 1009 " (trade mark of Shell Chemical Co. of 880g (0.5 mole), molecular weight is 3,750 Resins, epoxy) and 1,000g mixed solvent (methyl iso-butyl ketone (MIBK)/dimethylbenzene=1/1, weight ratio).Stirring down, the interior mixture of reactor heating obtains uniform solution.Solution is cooled to 70 ℃, drips 70g and be weighed to two in the dropping funnel (n-propyl alcohol) amine in surpassing 30 minutes.In the dropping process, temperature of reaction remains on 70 ℃.After drip finishing, reaction mixture kept 2 hours obtaining amino modified Resins, epoxy so that react and finish under 120 ℃ temperature, and its solids content is 66%.Per 1, the 000g resin adds 25 part 88% formic acid.Add after the water, thoroughly stir the mixture to obtain the amino modified Resins, epoxy dispersion liquid (C2) of water-based, its solids content is 30%.

The preparation of coating composition of the present invention

Embodiment 1

The preparation method that the present invention is used to form the coating composition of titanium dioxide film makes the titaniferous aqueous solution (1) that obtains in 50 parts of production examples 1,2 parts of 60%1-hydroxyl ethanes-1, and 1-di 2 ethylhexyl phosphonic acid and 48 parts of deionized waters mix.

Embodiment 2 to 19 and comparative example 1 to 2

Use the component in the table 1, the mode identical with embodiment 1 prepares coating composition of the present invention and control coatings composition.

Table 1

		Embodiment
													??1	??2	??3	??4	??5	??6	??7	??8	??9	??10	??11
		Component (A)	????(1)	??50
????(2)													??50						??50	??50	??50	??50
			????(3)			??50
????(4)															??50
			????(5)					??50
????(6)																	??50
			????(7)							??50
Component (B)	60%1-hydroxyl ethane-1, the 1-di 2 ethylhexyl phosphonic acid												??2	??2	??2	??2	??2	??2	??2						??2
		10% oxyacetic acid								????5
	10% oxysuccinic acid																				????5			??3
		10% citric acid										??5
	10% ortho-phosphoric acid
10% metaphosphoric acid
		40% hydrofluotitanic acid
30% water-borne acrylic resin dispersion liquid (C1)
		The amino modified Resins, epoxy dispersion liquid of 30% water-based (C2)
50%1, the 1-polyvinylidene chloride resin ( *1)
		10% polyvinyl alcohol ( *2)
The fine silica powder ( *3)
		Deionized water											??48	??48	??48	??48	??48	??48	??48	??45	??45	??45		??45

Table 1 (continuing)

		Embodiment								Comparative example
												??12	??13	??14	??15	??16	??17	??18	??19	??1	??2
		Component (A)	????(1)																			??50
????(2)	??50											??50	??50	??50	??50	??50	??50	??50		??50
			????(3)
????(4)
			????(5)
????(6)
			????(7)
Component (B)	60%1-hydroxyl ethane-1, the 1-di 2 ethylhexyl phosphonic acid											??2	??2	??2	??2	??2	??2	??2	??2
		10% oxyacetic acid
	10% oxysuccinic acid
		10% citric acid
	10% ortho-phosphoric acid											??5
10% metaphosphoric acid				??5		??5
		40% hydrofluotitanic acid												??1
30% water-borne acrylic resin dispersion liquid (C1)								??2
		The amino modified Resins, epoxy dispersion liquid of 30% water-based (C2)															??1
50%1, the 1-polyvinylidene chloride resin ( *1)										??1
		10% polyvinyl alcohol ( *2)																	??3
The fine silica powder ( *3)							??1
		Deionized water										??43	??43	??47	??42	??46	??47	??47	??45	??50		??50

In table 1, ^*1 arrives ^*3 are described as follows:

^*1: " Saran Latex L-411 ", the trade mark of Asahi Kasei Corp., solids content is 50% vinylidene chloride resin

^*2: " Kuraray RS Polymer RS-105 ", Kuraray Co., the trade mark of Ltd., solids content is 10% polyvinyl alcohol

^*3: " Aerosil 380 ", Nippon Aerosil Co., the trade mark of Ltd., a kind of pigment extender, a kind of specific surface area is 380m ²/ g and mean particle size are the fine silica powder of 7nm

The performance test of coating composition of the present invention

The coating composition that embodiment 1 to 19 and comparative example 1 and 2 are obtained is applied to metal base.The erosion resistance of the coating material that test obtains.

(1) coating of aluminium sheet

Thickness is that the aluminium sheet (A1050) of 0.1mm is with (product of Japan CB ChemicalCo., trade mark " Chemicleaner the 561B ") decontamination of 2% alkali stain remover and wash with water.Use coating composition by roller coat, so that dry film heavily is 0.2g/m ², to dry 20 seconds, drying condition is that base material temperature is 100 ℃, to form titanium dioxide film.

(2) erosion resistance of paint sheet

Paint sheet carries out brine spray experiment 120,240,360 and 480 hours by JIS Z2371 regulation, according to following grading evaluation.

A: coatingsurface does not have the rust or the bubble of white;

B: the rust of slight white or bubble;

C: the rust of serious white or bubble.

Table 2 expression test result.

Table 2

Coating composition	The test duration section
					????120hr	????240hr	????360hr	????480hr
	Embodiment 1	????a	????a	????a					????b
Embodiment 2					????a	????a	????a	????b
	Embodiment 3	????a	????a	????a					????b
Embodiment 4					????a	????a	????a	????b
	Embodiment 5	????a	????a	????a					????b
Embodiment 6					????a	????a	????b	????c
	Embodiment 7	????a	????a	????b					????c
Embodiment 8					????a	????a	????b	????c
	Embodiment 9	????a	????a	????b					????c
Embodiment 10					????a	????a	????b	????c
	Embodiment 11	????a	????a	????a					????b
Embodiment 12					????a	????a	????a	????b
	Embodiment 13	????a	????a	????a					????a
Embodiment 14					????a	????a	????a	????a
	Embodiment 15	????a	????a	????a					????a
Embodiment 16					????a	????a	????b	????c
	Embodiment 17	????a	????a	????b					????c
Embodiment 18					????a	????a	????b	????c
	Embodiment 19	????a	????a	????b					????c
Comparative example 1					????b	????c	????c	????c
	Comparative example 2	????b	????b	????c					????c

(3) coating of steel plate

Thickness is that (the galvanized amount of a side is: 20g/m for the electrogalvanizing steel plate of 0.6mm ²) with the aqueous solution decontamination of 2% alkali stain remover (product of Japan CB Chemical Co., trade mark " Chemicleaner 561B ") and wash with water.Use coating composition by roller coat, so that dry film heavily is 1.0g/m ², to dry 20 seconds, drying condition is that base material temperature is 100 ℃, to form titanium dioxide film.

(4) erosion resistance of paint sheet

Make the end face and the sealing backside of paint sheet.The plate that obtains carries out brine spray experiment 24,48 and 72 hours by JIS Z2371 regulation, according to following grading evaluation.

A: the rust that does not have white;

B: the rust that is less than 5% coatingsurface zone adularescent;

C: be no less than 5% but be less than the rust of 10% coatingsurface zone adularescent;

D: be no less than 10% but be less than the rust of 50% coatingsurface zone adularescent;

The rust of e:50% or more coatingsurface zone adularescent;

Table 3 expression test result.

Table 3

Coating composition	The test duration section
				????24hr	????48hr	????72hr
	Embodiment 1	????a	????a				????b
Embodiment 2				????a	????a	????b
	Embodiment 3	????a	????a				????b
Embodiment 4				????a	????a	????b
	Embodiment 5	????a	????a				????b
Embodiment 6				????a	????b	????c
	Embodiment 7	????a	????b				????c
Embodiment 8				????a	????b	????c
	Embodiment 9	????a	????b				????c
Embodiment 10				????a	????b	????c
	Embodiment 11	????a	????a				????b
Embodiment 12				????a	????a	????a
	Embodiment 13	????a	????a				????a
Embodiment 14				????a	????a	????a
	Embodiment 15	????a	????a				????a
Embodiment 16				????a	????b	????c
	Embodiment 17	????a	????b				????c
Embodiment 18				????a	????b	????c
	Embodiment 19	????a	????b				????c
Comparative example 1				????c	????d	????d
	Comparative example 2	????c	????c				????d

(5) coating of steel plate

Thickness is that (the galvanized amount of a side is: 20g/m for the electrogalvanizing steel plate of 0.6mm ²) regulate with 2% alkali stain remover decontamination and by " Preparen Z " (Nihon Parkerizing Co., trade mark of Ltd.) spraying plating.Steel plate is washed and the dry electroplating steel plate that obtains the zinc phosphate processing with " Palbond 3308 " (Nihon Parkerizing Co., the trade mark of Ltd., phosphoric acid zinc aqueous solution) spraying plating then.The amount that zinc phosphate is handled coating is 1.5g/m ²

By the electroplating steel plate surface applied coating composition of spraying, so that dry film heavily is 1.0g/m to the zinc phosphate processing ², to dry 20 seconds, drying condition is that to make base material temperature be 100 ℃, to form titanium dioxide film.

(6) erosion resistance of paint sheet

End face and sealing backside with paint sheet.The plate that obtains carries out brine spray experiment 24,48 and 72 hours by JIS Z2371 regulation, according to following grading evaluation.

A: the rust that does not have white;

B: the rust that is less than 5% coatingsurface zone adularescent;

C: be no less than 5% but be less than the rust of 10% coatingsurface zone adularescent;

D: be no less than 10% but be less than the rust of 50% coatingsurface zone adularescent;

The rust of e:50% or more coatingsurface zone adularescent;

Table 4 expression test result.

Coating composition	The test duration section
				????24hr	????48hr	????72hr
	Embodiment 1	????a	????a				????b
Embodiment 2				????a	????a	????b
	Embodiment 3	????a	????a				????b
Embodiment 4				????a	????a	????b
	Embodiment 5	????a	????a				????b
Embodiment 6				????a	????b	????c
	Embodiment 7	????a	????b				????c
Embodiment 8				????a	????b	????c
	Embodiment 9	????a	????b				????c
Embodiment 10				????a	????b	????c
	Embodiment 11	????a	????a				????b
Embodiment 12				????a	????a	????a
	Embodiment 13	????a	????a				????a
Embodiment 14				????a	????a	????a
	Embodiment 15	????a	????a				????a
Embodiment 16				????a	????b	????c
	Embodiment 17	????a	????b				????c
Embodiment 18				????a	????b	????c
	Embodiment 19	????a	????b				????c
Comparative example 1				????c	????d	????d
	Comparative example 2	????c	????c				????d

(7) formation of the undercoat of steel plate and external coating (EC)

Thickness be the surface of hot-rolled low carbon steel plate (SPCC-SD) of 0.6mm at 65 ℃ with the 2% alkali stain remover (product of Japan CB Chemical Co., trade mark " Chemicleaner561B ") the aqueous solution sprays decontamination 20 seconds, and sprays Warm Wash 20 seconds at 60 ℃.By spraying the steel plate of decontamination is used coating composition, so that dry film heavily is 1g/m ², dry 15 seconds (base material temperature becomes 100 ℃) down at 250 ℃, to form titanium dioxide film as undercoat.

The steel plate that undercoat is arranged is used " Amilac #1000 White " (Kansai Paint Co., the trade mark of Ltd., a kind of Synolac coating composition of thermosetting, white), so that dry film heavily is 20g/m ², dry 20 minutes formation external coating (EC)s down at 130 ℃, and as the test paint sheet.

(8) the test performance test of paint sheet

By the following method test is tested with the erosion resistance of paint sheet and the tackiness of external coating (EC).

Erosion resistance: the end face and the sealing backside that make paint sheet., make the intersection that reaches base material deeply with pocket knife and draw quarter with on the coatingsurface of paint sheet in each test, the plate that obtains carries out brine spray experiment 120 hours by JIS Z2371 regulation.After the test, each test is drawn quarter with the intersection on the paint sheet partly use sealing tape, and tear rapidly.Width according to following grading evaluation external coating (EC) released part:

A:1mm or littler;

B:1 is to 3mm;

C:3 is to 5mm;

D:5mm or bigger.

The external coating (EC) tackiness:, make of pocket knife and to reach drawing of base material deeply and carve with on the coatingsurface of paint sheet in each test, respectively 11 of vertical and levels form 100 squares (1mm * 1mm).Use sealing tape to drawing to carve partly, and tear rapidly.Then according to the extent of exfoliation of following grading evaluation external coating (EC):

A: basic nothing is peeled off;

B:1 or 2 squares are peeled off;

C:3 to 10 square peeled off;

D:10 or more squares are peeled off.

Table 5 expression test result.

Coating composition	Erosion resistance (120hr)	The external coating (EC) tackiness
			Embodiment 1	b	??a
Embodiment 2	b	??a
			Embodiment 3	b	??a
Embodiment 4	b	??a
			Embodiment 5	b	??a
Embodiment 6	c	??a
			Embodiment 7	c	??a
Embodiment 8	c	??a
			Embodiment 9	c	??a
Embodiment 10	c	??a
			Embodiment 11	b	??a
Embodiment 12	a	??a
			Embodiment 13	a	??a
Embodiment 14	a	??a
			Embodiment 15	a	??a
Embodiment 16	c	??a
			Embodiment 17	c	??a
Embodiment 18	c	??a
			Embodiment 19	c	??a
Comparative example 1	d	??b
			Comparative example 2	d	??b

The coating composition that is used to form titanium dioxide film of the present invention, form the technique of titanium dioxide film, and the metal base that scribbles titanium dioxide film has following remarkable result:

(1) coating composition of the present invention has excellent storage stability. This may be because the titaniferous aqueous solution (A) itself is stable, and forms stable complex compound with organic acid and/or its salt (B).

(2) technique of use coating composition of the present invention can form at metal base the film that contains amorphous titania of the character excellences such as corrosion resistance, adherence, durability, machinability, hydrophily.

Excellent corrosion resistance and the realization of durability may be because: film has good adherence to base material; Film is the compact titanium dioxide film, and its permeability to oxygen or steam is low; Organic acid and/or its salt (B) and metal base coordination, and play the effect of metal corrosion inhibitor; And titanium dioxide protection component (B). It may be because the titanium dioxide in the film comprises hydroxyl that film has high adherence.

(3) the coating metal base material that obtains of technique of the present invention can be advantageously used for the antitarnish coatings base material and need not further processing.

(4) heat exchanger fin that comprises the aluminum or aluminum alloy base material can be avoided the water bridge that formed by condensed water in the cooling down operation process, thereby and prevent corrosion, wherein aluminum or aluminum alloy scribbles by the formed film of coating composition of the present invention.

Claims (20)

1. coating composition that is used to form titanium dioxide film, it comprises (A) a kind of titaniferous aqueous solution, the titanium compound of the low condenses by making at least a low condenses, titanium hydroxide and the titanium hydroxide that is selected from hydrolyzable titanium compound, hydrolyzable titanium compound mixes with aqueous hydrogen peroxide solution and obtains and (B) at least a compound that is selected from organic acid and salt thereof.

2. the coating composition of claim 1, wherein the titaniferous aqueous solution (A) is a kind of pertitanic acid aqueous solution, obtains by hydrolyzable titanium compound and/or its low condenses are mixed with aqueous hydrogen peroxide solution.

3. the coating composition of claim 2, wherein the hydrolyzable titanium compound is four titan-alkoxides that are expressed from the next:

Ti(OR) ₄?????????(1)

Wherein R can be identical or different, represents C respectively ₁To C ₅Alkyl.

4. the coating composition of claim 2, wherein the low condenses of hydrolyzable titanium compound is that condensation degree is 2 to 30 compound, and the obtaining from condensation of four titan-alkoxides of representing by following formula:

Ti(OR) ₄?????????(1)

Wherein R can be identical or different, represents C respectively ₁To C ₅Alkyl.

5. the coating composition of claim 2, wherein the ratio of aqueous hydrogen peroxide solution is 0.1 to 100 weight part in the per 10 weight part hydrolyzable titanium compounds of hydrogen peroxide and/or its low condenses.

6. the coating composition of claim 2, wherein the titaniferous aqueous solution (A) is a kind of pertitanic acid aqueous solution, obtains by hydrolyzable titanium compound and/or its low condenses are mixed in the presence of TiO 2 sol with aqueous hydrogen peroxide solution.

7. the coating composition of claim 6, wherein TiO 2 sol is the aqueous dispersions of anatase titania.

8. the coating composition of claim 6, wherein the ratio of TiO 2 sol is 0.01 to 10 weight part in the per 1 weight part hydrolyzable titanium compound of solid and/or its low condenses.

9. the coating composition of claim 1, wherein compound (B) is at least a compound that is selected from hydroxycarboxylic acid, hydroxyl organic phosphorous acid, contains carboxyl organic phosphorous acid and these sour salt.

10. the coating composition of claim 1, wherein the per 100 weight part solid titaniferous aqueous solution (A) of the ratio of compound (B) are 1 to 400 weight part.

11. the coating composition of claim 1, it is the aqueous solution of pH1 to 10.

12. the coating composition of claim 11, it is the aqueous solution of pH1 to 9.

13. the coating composition of claim 1, it further comprises a kind of inorganic phosphate compound.

14. the coating composition of claim 1, it further comprises at least a halogenide that is selected from halogen metatitanic acid, halogen titanate, halogen zirconic acid, halogen zirconate, halogen silicic acid and halogen silicate.

15. the coating composition of claim 1, it further comprises the water-based organic high molecular compound.

16. a technology that is used to form titanium dioxide film, it comprises the coating composition of metal base being used claim 1, and is dry then.

17. a coating metal base material, it comprises a kind of metal base and the film of the coating composition of the claim 1 that forms on substrate surface.

18. the coating metal base material of claim 17, wherein the dry weight of film is 0.001 to 10g/m ²

19. the coating metal base material of claim 17, wherein metal base is formed from steel.

20. the coating metal base material of claim 17, wherein metal base is made by aluminum or aluminum alloy.